We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702-19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.Ab initio quantum Monte Carlo methods, in principle, allow for the calculation of exact properties of correlated many-electron systems but are, in general, limited to the simulation of a finite number of electrons N under periodic boundary conditions. Therefore, an accurate theory of finite-size effects is indispensable to bridge the gap to realistic applications in the thermodynamic limit. In this work, we revisit the uniform electron gas at finite temperature, as it is relevant to contemporary research, e.g., in the field of warm dense matter. In particular, we present a new scheme to eliminate finite-size effects both in the static structure factor S(q) and in the interaction energy v, which is based on the density response formalism. We demonstrate that this method often allows us to obtain v in the thermodynamic limit within a relative accuracy of ?0.2% from as few as N = 4 electrons without any empirical choices or knowledge of results for other values of N. Finally, we evaluate the applicability of our method upon increasing the density parameter rs and decreasing the temperature T.The interaction of ions and water at high pressure and temperature plays a critical role in Earth and planetary science yet remains poorly understood. Aqueous fluids affect geochemical properties ranging from water phase stability to mineral solubility and reactivity. Here, we report first-principles molecular dynamics simulations of mono-valent ions (Li+, K+, Cl-) as well as NaCl in liquid water at temperatures and pressures relevant to the Earth's upper mantle (11 GPa, 1000 K) and concentrations in the dilute limit (0.44-0.88 m), in the regime of ocean salinity. We find that, at extreme conditions, the average structural and vibrational properties of water are weakly affected by the presence of ions, beyond the first solvation shell, similar to what was observed at ambient conditions. We also find that the ionic conductivity of the liquid increases in the presence of ions by less than an order of magnitude and that the dielectric constant is moderately reduced by at most ?10% at these conditions. Our findings may aid in the parameterization of deep earth water models developed to describe water-rock reactions.Hybridization functions are an established tool for investigating the coupling between a correlated subsystem (often a single transition metal atom) and its uncorrelated environment (the substrate and any ligands present). The hybridization function can provide valuable insight into why and how strong correlation features such as the Kondo effect can be chemically controlled in certain molecular adsorbates. To deepen this insight, we introduce a local decomposition of the hybridization function, based on a truncated cluster approach, enabling us to study individual effects on this function coming from specific parts of the systems (e.g., the surface, ligands, or parts of larger ligands). It is shown that a truncated-cluster approach can reproduce the Co 3d and Mn 3d hybridization functions from periodic boundary conditions in Co(CO)4/Cu(001) and MnPc/Ag(001) qualitatively well. By locally decomposing the hybridization functions, it is demonstrated at which energies the transition metal atoms are mainly hybridized with the substrate or with the ligand. For the Kondo-active 3dx2-y2 orbital in Co(CO)4/Cu(001), the hybridization function at the Fermi energy is substrate-dominated, so we can assign its enhancement compared with ligand-free Co to an indirect effect of ligand-substrate interactions. In MnPc/Ag(001), the same is true for the Kondo-active orbital, but for two other orbitals, there are both direct and indirect effects of the ligand, together resulting in such strong screening that their potential Kondo activity is suppressed. A local decomposition of hybridization functions could also be useful in other areas, such as analyzing the electrode self-energies in molecular junctions.The capability of fewest-switches surface hopping (FSSH) to describe non-adiabatic dynamics under explicit excitation with external fields is evaluated. Different FSSH parameters are benchmarked against multi-configurational time dependent Hartree (MCTDH) reference calculations using SO2 and 2-thiocytosine as model, yet realistic, molecular systems. Qualitatively, FSSH is able to reproduce the trends in the MCTDH dynamics with (also without) an explicit external field; however, no set of FSSH parameters is ideal. https://www.selleckchem.com/products/ulixertinib-bvd-523-vrt752271.html The adequate treatment of the overcoherence in FSSH is revealed as the driving factor to improve the description of the excitation process with respect to the MCTDH reference. Here, two corrections were tested the augmented-FSSH (AFSSH) correction and the energy-based decoherence correction. A dependence on the employed basis is detected in AFSSH, performing better when spin-orbit and external laser field couplings are treated as off-diagonal elements instead of projecting them onto the diagonal of the Hamilton operator. In the presence of an electric field, the excited state dynamics was found to depend strongly on the vector used to rescale the kinetic energy along after a transition between surfaces. For SO2, recurrence of the excited wave packet throughout the duration of the applied laser pulse is observed for laser pulses (&gt;100 fs), resulting in additional interferences missed by FSSH and only visible in variational multi-configurational Gaussian when utilizing a large number of Gaussian basis functions. This feature vanishes when going toward larger molecules, such as 2-thiocytosine, where this effect is barely visible in a laser pulse 200 fs long.